WO2002068503A1 - Procédé perfectionné pour produire des polyéthers polyols - Google Patents

Procédé perfectionné pour produire des polyéthers polyols Download PDF

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Publication number
WO2002068503A1
WO2002068503A1 PCT/EP2002/001398 EP0201398W WO02068503A1 WO 2002068503 A1 WO2002068503 A1 WO 2002068503A1 EP 0201398 W EP0201398 W EP 0201398W WO 02068503 A1 WO02068503 A1 WO 02068503A1
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WO
WIPO (PCT)
Prior art keywords
dmc
polyol
catalyst
polyether polyols
polyaddition
Prior art date
Application number
PCT/EP2002/001398
Other languages
German (de)
English (en)
Inventor
Jörg Hofmann
Stephan Ehlers
Bernd Klinksiek
Lars Obendorf
Christian Steinlein
Bert Klesczewski
Jose F. Pazos
Original Assignee
Bayer Aktiengesellschaft
Bayer Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Aktiengesellschaft, Bayer Corporation filed Critical Bayer Aktiengesellschaft
Priority to AT02714155T priority Critical patent/ATE295861T1/de
Priority to KR1020037010984A priority patent/KR100799036B1/ko
Priority to BRPI0207766-3A priority patent/BR0207766B1/pt
Priority to MXPA03007533A priority patent/MXPA03007533A/es
Priority to HU0303259A priority patent/HU227020B1/hu
Priority to DE50203140T priority patent/DE50203140D1/de
Priority to EP02714155A priority patent/EP1368407B1/fr
Priority to JP2002568010A priority patent/JP4112985B2/ja
Priority to CA002438647A priority patent/CA2438647A1/fr
Publication of WO2002068503A1 publication Critical patent/WO2002068503A1/fr
Priority to HK04109847A priority patent/HK1066819A1/xx

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2696—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the process or apparatus used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1868—Stationary reactors having moving elements inside resulting in a loop-type movement
    • B01J19/1881—Stationary reactors having moving elements inside resulting in a loop-type movement externally, i.e. the mixture leaving the vessel and subsequently re-entering it
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
    • B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's

Definitions

  • the invention relates to an improved process for the preparation of polyether poly oils by means of double metal cyanide (DMC) catalysis by polyaddition of alkylene oxides onto starter compounds having active hydrogen atoms.
  • DMC double metal cyanide
  • polyether polyols are technically largely by polyaddition of alkylene oxides to polyfunctional starter compounds, such as Alcohols, acids, or amines carried out using base catalysis (e.g. KOH) (see e.g. Gum, Riese & Ulrich (ed.): "Reaction Polymers", Hanser Verlag, Kunststoff, 1992, SJ5-96).
  • base catalysis e.g. KOH
  • the basic catalyst must be removed from the polyether polyol in a very complex process, e.g. through neutralization, distillation and filtration.
  • the base-catalyzed polyether polyols also have the disadvantage that as the chain length increases, the content of monofunctional polyethers with terminal double bonds (so-called monools) increases steadily and the functionality decreases.
  • polyether polyols obtained can be used for the production of polyurethanes (e.g. elastomers, foams, coatings), in particular also for
  • Double metal cyanide (DMC) catalysts for the production of polyether polyols have long been known (see, for example, US Pat. Nos. 3,440,109, 3,829,505, 3,941,849 and 5,158,922).
  • DMC Double metal cyanide
  • the use of these DMC catalysts for the production of polyether polyols leads in particular to a reduction in the proportion of monofunctional polyethers (monools) compared to the conventional production of polyether polyols using basic catalysts.
  • Improved DMC catalysts as described, for example, in EP-A 700 949, EP-A 761 708, WO 97/40086, WO 98/16310, DE-A 197 45 120, DE-A 197 57 574 or DE-A 198 102 269 are also extremely active and enable the production of polyether polyols at a very low catalyst concentration (25 ppm or less), so that it is no longer necessary to separate the catalyst from the polyol.
  • the polyether polyols obtained by means of DMC catalysis can lead to application-related problems in the production of polyurethane foam, in particular flexible polyurethane foams, for example foam destabilization (increased susceptibility to collapse) or increased coarseness.
  • DMC-catalyzed polyether polyols can therefore not in all cases replace corresponding base-catalyzed polyols in flexible polyurethane foam applications without adapting the formulation.
  • polyether polyols which are produced entirely or partially by means of DMC catalysis have significantly improved foaming properties in the production of polyurethane foams if the polyether polyol is active during the DMC-catalyzed polyaddition of alkylene oxides
  • Starter compounds containing hydrogen atoms is passed through a suitable mixing unit.
  • the present invention thus relates to an improved process for the preparation of polyether polyols, in which the polyether polyol is wholly or partly by double metal cyanide-catalyzed polyaddition of alkylene oxides to active water Starter compounds having substance atoms is produced and in which the polyether polyol is passed through a suitable mixing unit during the DMC-catalyzed polyaddition.
  • the present invention further relates to the use of the polyether polyols thus obtained for the production of polyurethane foam, in particular flexible polyurethane foams.
  • DMC catalysts suitable for the process according to the invention are known in principle.
  • DMC catalysts such as those described in JP-A 4 145 123, EP-A 654 302, EP-A 700 949, EP-A 743 093, EP-A 761 708, WO 97/40086, WO 98/16310 are preferably used , WO 99/19062, WO 99/19063, WO 99/33562,
  • a typical example are the highly active DMC catalysts described in EP-A 700 949, which, in addition to a double metal cyanide compound (for example zinc hexacyanocobaltate (Hi)) and an organic complex ligand (for example tert-butanol), also a polyether polyol with a number average molecular weight greater than 500 contain g / mol.
  • a double metal cyanide compound for example zinc hexacyanocobaltate (Hi)
  • an organic complex ligand for example tert-butanol
  • starter compounds with active hydrogen atoms compounds with molecular weights of 18 to 2,000 g / mol, preferably 62 to 1,000 g / mol and 1 to 8, preferably 2 to 6, hydroxyl groups are preferably used.
  • Examples include butanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenol-A, trimethylolpropane, glycerol, pentaerythritol, sorbitol, cane sugar, degraded starch, water or so-called pre-extended starters, which are obtained from the aforementioned compounds by alkoxylation.
  • Preferred alkylene oxides are ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.
  • the structure of the polyether chains can be carried out diu-ch with only one monomeric epoxide or can also be carried out randomly or in blocks with 2 or 3 different monomeric epoxides. More details are "Ullmanns
  • a conventional batch process can be used.
  • the DMC catalyst and the starter compound are placed in a batch reactor, then the reactor is heated to the desired temperature and a sufficient amount of alkylene oxide is added to activate the catalyst.
  • the catalyst is activated, e.g. is noticeable by a pressure drop in the reactor, the remaining alkylene oxide is metered in continuously until the desired molecular weight of the polyether polyol is reached.
  • a continuous process can also be used in which a pre-activated mixture of DMC catalyst and starter compound is continuously fed to a continuous reactor, e.g. a continuous stirred reactor (CSTR) or a tubular reactor is fed. Alkylene oxide is metered into the reactor and the product is continuously removed.
  • a continuous reactor e.g. a continuous stirred reactor (CSTR) or a tubular reactor is fed. Alkylene oxide is metered into the reactor and the product is continuously removed.
  • the DMC-catalyzed polyaddition is preferably carried out by a process in which the starter compound is metered in continuously during the polyaddition.
  • the DMC-catalyzed polyaddition with continuous starter metering can be carried out according to a batch process as taught in WO 97/29146 or a continuous process as shown in WO 98/03571.
  • the DMC-catalyzed polyaddition can take place at pressures from 0.0001 to 20 bar, preferably from 0.5 to 10 bar, particularly preferably from 1 to 6 bar.
  • the reaction temperatures are 20 to 200 ° C, preferably 60 to 180 ° C, particularly preferably 80 to 160 ° C.
  • the DMC catalyst concentration is generally 0.0005 to 1% by weight, preferably 0.001 to 0.1% by weight, particularly preferably 0.001 to 0.01% by weight, based on the amount of the polyether polyol to be produced.
  • the polyether polyol is passed through a zone with high energy density during the DMC-catalyzed polyaddition, as occurs, for example, in a suitable mixing unit.
  • suitable mixing units for the treatment of the polyether polyols according to the invention will be described below.
  • Suitable mixing units are characterized by the fact that, due to their geometry, they enter a high local energy density in the form of flow energy into the product. Since high pressures are often used for this task, these mixing units are also referred to as high-pressure homogenizers. Mixing units that are particularly suitable for such tasks are static mixers and / or
  • Jet aggregates Simple perforated orifices, flat nozzles, serrated nozzles, knife edge nozzles, microfluidizers, as described in US Pat. No. 4,533,254, microstructure mixers, microstructure components or jet dispersers are particularly suitable. Other geometries that work on the same principle of this or other nozzle assemblies are easily accessible to the person skilled in the art. The functional principle of these nozzle assemblies is explained using the example of a simple pinhole. The product stream is pressurized by a pump and expanded through the orifice. Due to the sudden narrowing of the cross-section, the product flow in the nozzle is greatly accelerated. Depending on the geometry of the panel, two types of force can act on the product. Either the product flow is accelerated so much that the flow in the nozzle is turbulent, or, in the case of a laminar flow, a so-called expansion flow occurs in the nozzle.
  • FIG. 1 shows a flat nozzle
  • Fig. 2 a knife edge nozzle is shown
  • a microfluidizer is shown in FIG.
  • a prong nozzle is shown
  • Fig. 5 a jet disperser is shown.
  • mixing units which enter a high energy density in the form of flow energy into the product
  • devices are also suitable, which bring in a high energy density through rotating parts, e.g. Rotor-stator systems, ball mills, colloid mills, wet rotor mills, gear rim dispersing machines, intensive mixers, which use the principle of the gear rim dispersing machines but are flowed through in the axial direction, or other apparatus using rotating parts, which are easily accessible to the person skilled in the art and for which task can be used.
  • rotating parts e.g. Rotor-stator systems, ball mills, colloid mills, wet rotor mills, gear rim dispersing machines, intensive mixers, which use the principle of the gear rim dispersing machines but are flowed through in the axial direction, or other apparatus using rotating parts, which are easily accessible to the person skilled in the art and for which task can be used.
  • Ultrasonic disintegrators generate high energy densities through cavitation.
  • Cavitation is understood to mean the formation and collapse of vapor bubbles in a liquid in which an isothermal pressure drop first occurs up to the vapor pressure of the liquid and the pressure then rises again. The resulting gas bubbles collapse again due to the pressure increase. During the collapse process, the crushing energy is released.
  • the necessary energy density can also be achieved in this way with polyethers.
  • the energy density E v is determined by the pressure difference (homogenizing pressure) ⁇ p ⁇ effective at the nozzle:
  • the energy density can be calculated experimentally from the power P, the density p, the dispersing volume V sp and the residence time t in this volume:
  • energy densities of at least 1 ⁇ 10 5 J / m 3 preferably at least 3 ⁇ 10 5 J / m 3 and particularly preferably at least 5 ⁇ 10 5 J / m 3 should be used.
  • Energy densities should be at least 1 x 10 "6 seconds. Usually it will be 1 x 10 " 5 to 1 second.
  • the polyol is sent through at least one high energy density zone at least once. As a rule, however, several passes through the mixing unit are realized.
  • the mixing units must be installed in such a way that they intervene directly in the alkoxylation process.
  • the mixing units can, for example, be introduced into a pumping circuit of the reactor.
  • the polyether polyol is passed through the mixing units together with the unreacted starter, alkylene oxide and catalyst. The addition of the reactants and the catalyst can take place independently of this mixing unit at a different point in the reactor.
  • nozzles and orifices are preferably installed in the pumping circuit, and jet dispersers are particularly preferably used.
  • the energy density required to achieve the desired effect is independent of the reactor pressure.
  • the only decisive factor is the energy density in the nozzle or orifice, which is proportional to the pressure loss in front of the nozzle or orifice.
  • the mixing units are used directly for mixing the feed streams with the reactor contents. Jet dispersers are particularly suitable for this task because they generate high energy densities, which means that the components can be mixed extremely quickly.
  • the starting materials for example 1. a starter mixture which contains either only one component or a mixture of various suitable compounds with active hydrogen atoms, 2. an alkylene oxide or a mixture of
  • Alkylene oxides and, optionally, 3. a catalyst suspension are homogenized in any suitable manner under conditions under which they do not react with one another and then mixed in the jet disperser with the polyether polyol contained in the active DMC catalyst.
  • suitable means that a homogeneous catalyst dispersion is obtained.
  • the starting materials are mixed with the polyether polyol contained in the active DMC catalyst using suitable mixing units in any order, if possible in short intervals.
  • suitable mixing units in any order, if possible in short intervals.
  • a plurality of nozzles connected in series are preferably used for this process control, with a number of jet dispersers connected in series being particularly preferred are preferred.
  • the order of the reactants added is not essential for achieving the object of the invention. It is preferred to first meter in the alkylene oxide or the mixture of alkylene oxides and then the starter mixture, which either contains only one component or a mixture of various suitable compounds with active hydrogen atoms, because of these
  • a possible deactivation of the active catalyst is prevented by an excessive local concentration of low molecular weight starter compounds. There is no preference for adding the catalyst.
  • the treatment of the polyether polyol with the mixing unit is generally carried out at temperatures from 20 to 200 ° C., preferably 60 to 180 ° C., particularly preferably 80 to 160 ° C.
  • the polyether polyol is produced entirely or partially by double metal cyanide-catalyzed polyaddition of alkylene oxides onto starter compounds having active hydrogen atoms.
  • any alternative (acidic, basic or coordinative) catalysts can be used to further build up the polyether polyol.
  • oligomeric alkoxylation products with number average molecular weights of 200 to 2,000 g / mol as starter compounds for DMC catalysis.
  • These can be achieved by alkoxylation of low molecular weight starter compounds such as e.g. 1,2-propylene glycol or glycerin can be produced using conventional base catalysis (e.g. KOH) or acid catalysis.
  • the so-called EO cap in which, for example, poly (oxypropylene) polyols or poly (oxypropylene / oxyethylene) polyols are reacted with ethylene oxide in order to convert the majority of the secondary OH groups of the polyether polyol into primary OH Converting groups is preferably carried out using base catalysis (eg KOH).
  • base catalysis eg KOH
  • the polyether polyols are preferably prepared in the process according to the invention in such a way that at least 20% by weight, preferably at least 40% by weight (based in each case on the amounts of the alkylene oxide used to prepare the polyethene polyol) of the alkylene oxide used is reacted by means of DMC catalysis become.
  • the polyethene polyols produced by the process according to the invention have significantly improved foaming properties in the production of flexible polyurethane foams.
  • Polyol A is a nominally trifunctional Polyethe ⁇ olyol with a molecular weight of 3,000 g / mol, which by reacting glycerol with propylene oxide by means of KOH catalysis (0.41 wt .-%, based on the amount of the finished Polyethe ⁇ olyols) at 107 ° C and subsequent separation of the Catalyst was obtained by neutralization with sulfuric acid, dewatering and filtration.
  • Polyol B is a nominally trifunctional polyethene polyol with a molecular weight of 3,000 g / mol, which is obtained by reacting glycerol with propylene oxide while continuously dosing the starter compound using DMC catalysis (30 ppm, based on the amount of the finished polyethene polyol, a zinc hexacyanocobaltate DMC catalyst , which contains tert-butanol as ligand and a poly (oxypropylene) diol obtained by DMC catalysis with a number-average molecular weight of 4000 g / mol, described in EP-A 700 949, Example 1), was obtained at 130 ° C. ,
  • Polyol C is a nominally trifunctional polyethene polyol with a molecular weight of 3,000 g / mol, which is obtained by reacting glycerol with propylene oxide while continuously metering the starter compound using DMC catalysis (30 ppm, based on the amount of the finished polyethene polyol of a zinc hexacyanocobaltate DMC catalyst). which contains tert-butanol as ligand and a poly- (oxypropylene) diol obtained by DMC catalysis with a number-average molecular weight of 4000 g / mol, described in EP-A 700 949, Example 1), was obtained at 130 ° C.
  • TDI mixture of isomers of 2,4-toluene diisocyanate and 2,6-diisocyanate in a ratio of 80:20, commercially available under the name Desmodur ® T80 (Bayer AG, 51368 Leverkusen, Germany)
  • Catalyst 1 bis (dimethylamino) ethyl ether
  • Silicone stabilizer 1 Tegostab ® BF 2370 (Th. Goldschmidt AG, D-45127 Essen)
  • Catalyst 2 tin octoate catalyst, commercially available as Desmorapid
  • Silicone stabilizer 1 0.6
  • the treatment according to the invention of the DMC-catalyzed polyol with the jet disperser gives a product (polyol C) which, in contrast to the untreated product (polyol B), can be processed without problems to give a flexible polyurethane foam.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Toxicology (AREA)
  • Polyethers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Cephalosporin Compounds (AREA)

Abstract

L'invention concerne un procédé perfectionné pour produire des polyéthers polyols par catalyse de cyanure métallique double (DMC) avec polyaddition d'oxydes d'alkylène sur des liaisons d'amorçage contenant des atomes d'hydrogène actifs.
PCT/EP2002/001398 2001-02-22 2002-02-11 Procédé perfectionné pour produire des polyéthers polyols WO2002068503A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
AT02714155T ATE295861T1 (de) 2001-02-22 2002-02-11 Verbessertes verfahren zur herstellung von polyetherpolyolen
KR1020037010984A KR100799036B1 (ko) 2001-02-22 2002-02-11 폴리에테르 폴리올의 개선된 제조 방법
BRPI0207766-3A BR0207766B1 (pt) 2001-02-22 2002-02-11 processo aperfeiÇoado para a preparaÇço de poliÉter-poliàis.
MXPA03007533A MXPA03007533A (es) 2001-02-22 2002-02-11 Procedimiento mejorado para preparacion de polioleteres.
HU0303259A HU227020B1 (en) 2001-02-22 2002-02-11 Improved method for producing polyether polyols
DE50203140T DE50203140D1 (de) 2001-02-22 2002-02-11 Verbessertes verfahren zur herstellung von polyetherpolyolen
EP02714155A EP1368407B1 (fr) 2001-02-22 2002-02-11 Procédé perfectioné pour produire des éthers de polyol
JP2002568010A JP4112985B2 (ja) 2001-02-22 2002-02-11 改良されたポリエーテルポリオールの製造方法
CA002438647A CA2438647A1 (fr) 2001-02-22 2002-02-11 Procede perfectionne pour produire des polyethers polyols
HK04109847A HK1066819A1 (en) 2001-02-22 2004-12-13 Improved method for producing polyether polyols

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10108484A DE10108484A1 (de) 2001-02-22 2001-02-22 Verbessertes Verfahren zur Herstelung von Polyetherpolyolen
DE10108484.6 2001-02-22

Publications (1)

Publication Number Publication Date
WO2002068503A1 true WO2002068503A1 (fr) 2002-09-06

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Application Number Title Priority Date Filing Date
PCT/EP2002/001398 WO2002068503A1 (fr) 2001-02-22 2002-02-11 Procédé perfectionné pour produire des polyéthers polyols

Country Status (19)

Country Link
US (1) US6776925B2 (fr)
EP (1) EP1368407B1 (fr)
JP (1) JP4112985B2 (fr)
KR (1) KR100799036B1 (fr)
CN (1) CN1215104C (fr)
AT (1) ATE295861T1 (fr)
BR (1) BR0207766B1 (fr)
CA (1) CA2438647A1 (fr)
CZ (1) CZ297775B6 (fr)
DE (2) DE10108484A1 (fr)
ES (1) ES2242003T3 (fr)
HK (1) HK1066819A1 (fr)
HU (1) HU227020B1 (fr)
MX (1) MXPA03007533A (fr)
PL (1) PL207572B1 (fr)
PT (1) PT1368407E (fr)
RU (1) RU2301815C2 (fr)
TW (1) TWI232228B (fr)
WO (1) WO2002068503A1 (fr)

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US7060647B2 (en) 2001-07-16 2006-06-13 Shell Oil Company Double metal complex catalyst
US9771451B2 (en) 2014-01-24 2017-09-26 Covestro Deutschland Ag Method for producing polycarbonate according to the phase interface method

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EP1369448A1 (fr) * 2002-06-07 2003-12-10 Bayer Ag Procédé pour la production de polycondensates et leur utilisation
CN1320029C (zh) * 2005-05-31 2007-06-06 抚顺佳化聚氨酯有限公司 一种聚醚多元醇的制备方法
DE102008012613A1 (de) 2008-03-05 2009-09-10 Bayer Materialscience Ag Verfahren zur Herstellung von Polycarbonat nach dem Phasengrenzflächenverfahren
WO2011043348A1 (fr) * 2009-10-05 2011-04-14 旭硝子株式会社 Procédé de fabrication d'une mousse souple de polyuréthane et siège
WO2012006264A1 (fr) * 2010-07-08 2012-01-12 Dow Global Technologies Llc Polyuréthanes fabriqués en utilisant des catalyseurs au zinc
JP5734633B2 (ja) * 2010-12-09 2015-06-17 三井化学株式会社 アルキレンオキサイド付加物の製造方法
US8663565B2 (en) * 2011-02-11 2014-03-04 Xerox Corporation Continuous emulsification—aggregation process for the production of particles
GB201810380D0 (en) * 2018-06-25 2018-08-08 Rosehill Polymers Group Ltd Continuous reaction system,vessel and method
EP3719052B1 (fr) 2019-04-03 2022-03-02 Covestro Deutschland AG Procédé de production de polycarbonate à excès réduit de phosgène

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US6776925B2 (en) 2004-08-17
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BR0207766B1 (pt) 2011-07-26
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